Pine-oil product and process of making same



, contain approximately ten" ")er cent of the which Patented Dec. 20,1927.

UNITED STATES TENT OFFICE.

IRVIN W. HUMPHR-EY, OF KENYIL, NEW JERSEY, ASSIGNOR TO HERCULES POWDER COMPANY, OF WILMINGTON, DELAWARE, A CORPORATION OF DELAWARE.

PINE-OIL rnonvczr AND rnocnss or MAKING SAME.

No Drawing.

The object of my invention is to provide a nitrocellulose lacquer or varnish; Another object of my invention is to provide a nitrocellulose lacquer containing an ingredient which will serve to some extent as a substitute for castor oil and other substances which are used 'to produce films of high fiexlbillty.

Another object of the invention is to produce a nitrocellulose lacquer ingredient which may be used as a substitute, in whole or in part, for amyl or butyl acetates and can be produced more cheaply, thereby effecting a'saving in the cost of manufac-' turing the lacquer.

Pine oil is known to be a complex mix ture of different substances, including terpineol, methyl chavicol, borneol, fenchyl alcohol, terpene hydrocarbons andsmaller amounts of several other bodies. Pine oil itself has no colloiding action upon nitrocotton, and its individual constituents also possess little colloiding power. However, certain of these constituents, notably borneol and fenchyl alcohol, yield, on oxidation, the

ketones camphor and fenchone' respectively, the former being a well known colloiding agent for nitrocellulose.

'Pine oil contains above five per 'cent of borneol, and approximately as much fenchyl alcohol. These two alcohols cannot be easily isolated frompine oil in a high degree, of purity by means of fractionation because of .the nearness oftheir boiling points with those of some of the other constituents of pine oil.

As set forth in an application filed by me November 22, 1924, Serial No. 751,682, I have found that it is feasible to treat pine oil with certain oxidizing agentsand obtain a liquid, which may be designated oxidized pine oil, which exhibits considerable colloid.-

-ing action on nitrocellulose. When pine oil is oxidized under proper conditions, it may ducted that a great portion of the pine oil Application filed August 17, 1925. Serial No. 50,839.

remains unaltered, serving as a diluent to the active colloiding agents but possessing a strong solventvpower for resins.

. A solution ofnitrocellulose may be prepared in straight oxidized pine oil, but on account of the rather high boiling range of It is possible to incorporate a large proportion of a non-solvent in the vehicle without precipitating the nitrocellulose. Alcohol, even if it contains as much as five per cent of water, is found to be a desirable diluent from the standpoint of increasing thecollcfnding action of oxidized pine oil. Even 1 as are added, the colloidiug action-of oxidized much as several'volumesof alcohol pine oil is accelerated to a'rem'a'rkable degree.

Several oxidizing ployed in Nitric acid is tion of pine hol. Sodium or potassium bichromate, or chromic acid, is preferable in some respects to nitric acid, since the latter converts much of the pine oil into undesired products. I have employed other oxidizing agents such as chlorine, potassium pcri'nangante and sodium hypochlorite, as. well.

According to one method of oxidizing pine oil, as described in my said application, the pine oil is treated with 4.2 times its weight of an'oxidizing mixture consisting of 15% sodium bichromate, 20% of sulfuric acid of 60 .136. and (35% of water, but different proportions of the oxidizing agent, as Well as 'varying amounts of acid and water, may be employed, Agitation is employed at a temperature of 21-32 0.,- with-some cooling, since the reaction is exothermic, but the temperature may be allowed to rise'somewhat higher. The crude oxidized oil is then re- -finedby a steam distillation.

The invention forming the subject of the present application has for its object to agents have been em-f preparing oxidized pine oil.

well adapted for u'seon a fracoil that is rich in fenchyl al'co- A produce oxidized pine oil products having a relatively low boiling range. It comprises in part matter divided out of said earlier application andin part is an improvement or modification of the subject-matter of said earlier application,

In said earlier application it is stated that treating oxidized pine oil with'a suitable dehydrator results in the conversion of a large part (say 60 percent) of the oxidized pine oil into a lower boiling product, which, if desired, may be distilled off, leav: ing a residue comprising ofthe original pine oil; As a typical example, it is stated that pine oil, oxidized as described, is. heated for one and one-half hours to 150 C. with two per cent of fullers earth. The fullers earth is then separated from the liquid, and the latter is distilled and collected in one lot. The product may be designated type A. It may be used in lacquers in much the same'manner as any 'other oxidized pine 011,

being blended with nonsolvent diluents and permissibly with Oxidized pine 011 Type A over at .f 186 176 over at 1 198 180 0 over at" 208 186 70 0 over at 210 190 0 over at 215 210 They differ chemically chiefly in the fact other nitrocellulose solvents.

The advantages of type oxidized pine oil are: 1) Greater volatility.

A over simple 2) Better solvent action on nitrocellulose in certainsolvent mixtures.

(3) Greater freedom from lacquers.

It is, however, a poorer solvent for certain resins than straight oxidized pine oil.

The following is a comparison of the boiling ranges of typical samples of oxidized pine oil and type A- blushing in that part or all of the alpha-terpineol (b. p.

in action, on nitrocellulose.

218 C.) .in oxidized pine. oil is converted into lower boilin These lower boilin substances consist largely of terpene hy rocarbons, dipentene and others. The alpha-terpineol whichis present in oxidized pine oil has little colloid.- The active col- I lolding ingredients in oxidized pine oil (camphor, fenchone, etc.) are not injured if the dehydration treatment isproperly applied.

' An alternative way of preparing type A comprises the following steps:

(a) The pine oil is treated with a dehydrating agent, thereby converting all or part of its terpuieol content into lower boiling about 35 per centsubstances (b. p. 170-185. C.) when type A is prepared. I

' understood that I mean to point substances, but with a minimum amount of dehydration of the remaining constituents.

(b) Forty to seventy-five per cent of the product is removed by ably by using a fractionating column.

(0) The residual pine oil is oxidized in the manner set forth in my earlier applica-' tion and as hereinbefore described or in any other efficient way.

I (cl) The oxidized residual pine oil is then refined by steam distillation. p 4

(e) The refined oxidized residual pine oil may be then added to part or'tall of the distillation, preferdistillate from step (7)), thereby obtaining.

the product. hereinbefore designated: as type A having a boiling range approximating that hereinbeforc speci tied for type A. e

However, the oxidized resldual pine oil resulting from step (a) Y may be employed alone,

O-ne'particular way of practicing the modified process just describedis as follows: The pine oil is heated to 145 C. for one hour with one and one-half per cent of fullers earth; After separatingthe fullers earth,

sixty per cent of the charge'is distilled oif through'a fractionating column.. The residue is then oxidized as hereinbefore described.- The crude product is refined by steam distillation and is then blended wit the first distillate.

It should -be stated that in referring to a dehydrator or dehydrating agent, I intend to include any reagent, some .of which are hereinafter-mentioned, whose chief effect is that offsplitting off chemically combined water from certain. of the pine oil c0nstitu-' ents, notably terpineoL' A wide variety of dehydrators may be employed ineither de- 1S preferable to use scribed method, but it the terpineol without one which decomposes attacking the other constituents. If the see I v I ond describedmethod is employed, somewhat more care is necessary 1n carrylng out the.

ile, in the foregoing description, I

,have described the process as starting with pine oil as the raw material, it should be include, as an equivalent for pine oil, the lay-product oil I which is obtained in preparing terpin 11y dr'ate from pine 011.

The foregoing discussion of methods of dehydratlon applies to. dehydration in the sirable,

oil, to add rather large proportions of lower liquid phase. Dehydration of the pineoil, before or after oxidation, may also be carried out in the vapor phase by passing the vapors over heated aluminum oxide, phosphoric acid on coke, or any of the catalysts which are employed'in the dehydration ofcapacity to dissolve certain resins, all the advantages of oxidized pine oil products produced by simple oxidation of their oxidizable constituents, and in addition have the adwhat I claim and vantages, hereinbefore mentioned, of greater volatility, better solvent action onnitrocellulose in certaln solvent mlxt'ures, and

greater freedom from blushing in lacquers;

and are therefore preferred by many users.

\Vhere reference is made to a nitrocellulose lacquer, I do notmean to include only those acquers which contain resins, as the oxidized product is also applicable as a nitrocellulose solvent when resinsare not present in the solution, and in fact, in the latter case, the product embodying my invention is of special advantage.

WVhen, in the claims coveringmy new process, I specify-certain steps, particularly oxidation and dehydration, I do not mean to be confined to practicing the steps in the orderrecited, except in those claims where the language is obviously intended to be limited to the order in which the steps are practiced.

Having now fully described my invention,

desire to protect by Letters Patent is: I

1. A pine oil product adapted for. use in preparing a solvent for nitrocellulose, comprising dehydrated constituents and oxidized constituents of pine oil adapted to have a substantial colloiding action on nitrocellulose.

2. A pine oil product adapted for use in preparing a solvent for nitrocellulose, ,comprising dehydrated constltuents and 0x1- dized constituentis of pine oil adapted-to have a substantia colloiding action on nitrocellulose, and inert constituents acting as a diluent.

3. A pine oil prising dehydrated constituents and oxidized constituents of pine oil adapted to cellulose, and a diluent having a substanproportion of oxidized inert- Q pine l.

product adapted for use in. preparing a solvent for nitrocellulose, comtially lower boiling range than the boiling range of oxidized pine oil.

4. A pine oil product adapted for use in preparing a solvent for nitrocellulose, comprising dehydrated constituents and oxidized constituents of pine oil adapted to have a substantial colloiding action on nitrocellulose, a diluent liquid having a substantially lower boiling range than the boiling range of oxidized pine oil, and inert constituents of pine oil also acting as a diluent. 5. A pine oil product adapted for use in preparing a solvent for nitrocellulose comprising dehydrated constituents and oxidized pine oil adapted to have a substantial colloiding action on nitrocellulose and the preponderating proportion of whose constituents has a boiling range of approximately 175220 C.

6. The process of preparing pine oil for use 1n the preparation of a nitrocellulose lacquer which comprises subjecting pine,oil

to two treatments: Namely, treatment with a dehydrating agent to convertcertain constituents into a lower boiling product, and

'treati'ngwith an agent eifective to oxidize certain oxidizable constituents of the pine oil.

' 7. The process of preparing pine oil for use in the preparation of a nitrocellulose solvent, which comprises subjecting pine oil totwo treatments: N amely, treatment with a dehydrating agent to convert certain constituentsinto a lower boiling product followed by distillation, and treating with an agent effective to oxidize certain oxidizable constituents of the pine oil followed by distillation.

8. The-process of preparing pine oil for use in the preparation of a nitrocellulose 'solvent, which comprises first treating pine oil with a dehydrating agent toicon'vert certain constituents thereof into a lower boiling product, and then treating the dehydrated product with an agent effective to oxidize certain oxidizable constituents thereof.

9. The process of preparing pine oil for use in the preparation of a nitrocellulose solvent, which comprises first treating pine oil with a dehydrating agent 'to convert certain constituents thereof into a lower boilingproduct, thendistilling off a substantial percentage of the dehydrated product, then treating the residual product with an agent efl'ective to oxidize certain oxidizable con-' stituents thereof, and then refining the oxidized product by distillation.

10. The 'process' ofpreparing pine oil for use in the preparation of a nitrocellulose effective to oxidize certain oxidizable constituents thereof, and then blending the oxidized product with said distillate. I

11. The process of preparing pine oil for use in the preparation of a nitrocellulose solvent, which comprises first treating pine oil with a dehydrating agent to convert certain constituents thereof into a lower boiling product, then distilling off a substantial percentage of-the dehydrated product, then treating the residual product with an agent efl'ective to oxidize certain oxidizable constituents thereof, then refining the oxidized product by distillation, and then blending the refined residue with distillate produced in the second of the foregoing steps.

In testimony of which invention, I have hereunto set my hand at Kenvil, New Jersey, on this 12th day of Aug, 1925. i

IRVIN W. HUMPHREY. 

